Although, many of these compounds are known per se, the literature does not indicate that they show fungicidal properties. The general methods for synthesising these compounds are described in Houben-Weyl, Vol. XII/2, pages 99 to 102.
The most widely used synthesis comprises reacting an optionally cyclic diester chloride of phosphorous acid with a primary or secondary amine in a solvent medium in accordance with the method developed by LUCAS, MITCHELL, SCULLY (J. Am. Chem. Soc. 72, pp. 5491-6/1950 ). 2-(N,N-dimethylamino)-1,3,2-dioxaphospholane for example may be prepared in this way.
23.5 G (0.2 M) of 2-chloro-1,3,2-dioxaphospholane are dissolved in 100 ml of petroleum ether. The solution is cooled to below 20.degree. C. and 18 g (0.4 M) of dimethylamine dissolved in 50 ml of petroleum ether are run in while stirring, the temperature being kept between -20.degree. and -10.degree. C. After the dimethylamine solution has been run in, the temperature is allowed to rise again and the dimethyl ammonium hydrochloride is filtered. The petroleum ether is removed, leaving an oil which is distilled in a water-jet pump vacuum.
b.p..sub.15 : 64.degree.-66.degree. C., n.sub.D.sup.20 = 1.4715, yield: 67 %
______________________________________ Analysis C % H % N % P % Calculated 35.6 7.42 10.32 22.95 Found 35.76 7.18 10.33 22.88 ______________________________________
The compounds whose characteristics are shown in the following Table were similarly prepared:
______________________________________ Physical Compounds characteristics Yield ______________________________________ O,O-diethyl-N,N-diethyl- b.p.:70- 80.degree.C./15mmHg 22 % aminophosphite 2-(N,N-diethylamino)-1,3,2- b.p.:87- 88.degree.C./16mmHg 58 % dioxaphospholane n.sub.D.sup.20 = 1.469 2-(N-isopropylamino)-1,3,2- b.p.:75.degree. C./15mmHg 47 % dioxaphospholane n.sub.D.sup.20 = 1.469 2-(N,N-diisopropylamino)- b.p.:95- 97.degree.C./15mmHg 27 % 1,3,2-dioxaphospholane n.sub.D.sup.20 = 1.464 2-(N,N-diallylamino)-1,3,2- b.p.:105.degree. C./14mmHg 62 % dioxa-phospholane 2-(1-piperidyl)-1,3,2-dioxa- b.p.:62- 64.degree.C./0.04mmHg 63 % phospholane 2-(1-morpholinyl)-1,3,2-dioxa- b.p.:116- 117.degree.C./7mmHg 67 % phospholane m.p.: 32-32.5.degree.C 2-(N,N-diethylamino)-4- b.p.86- 87.degree.C./13mmHg 64 % methyl-1,3,2-dioxaphospholane n.sub.D.sup.20 = 1.461 2-(1-morpholinyl)-4-methyl- b.p.117- 120.degree.C./10mmHg 40 % 1,3,2-dioxaphospholane n.sub.D.sup.20 = 1.4928 2-(N,N-diethylamino)-4-methoxy b.p.77.degree. C./0.2mmHg 80 % methyl-1,3,2-dioxaphospholane n.sub.D.sup.20 = 1.4649 2-N,N-(diethylamino)-4,5-benzo- b.p.:68- 76.degree.C./0.04mmHg 78 % 1,3,2-dioxaphospholane n.sub.D.sup.20 = 1.5318 2-(N,N-diethylamino)-1,3,2- b.p.:87.degree. C./15mmHg 61 % dioxaphosphorinane 2-(N,N-di-n-butylamino)-5,5- b.p.:84.degree. C./0.01mmHg 73 % dimethyl-1,3,2-dioxa- n.sub.D.sup.20 = 1.4655 phosphorinane ______________________________________
These compounds may form complexes with certain metal salts. The fungicidal application of these complexes is also part of the invention. Thus, a complex of cuprous chloride and 2-(N,N-diethylamino)-1,3,2-dioxaphospholane was prepared as follows:
1.0 g of cuprous chloride is added under a CO.sub.2 atmosphere to 1.6 g of 2-(N,N-diethylamino)-1,3,2-dioxaphospholane. The temperature of the mixture rises to 100.degree. C. Recrystallisation from alcohol gives 0.9 g of a white product. Yield: 35 %, m.p. 121.degree.-122.degree. C.
______________________________________ Centesimal analysis for C.sub.6 H.sub.14 ClCuNO.sub.2 P ______________________________________ % Cl P Calculated 13.53 11.81 Found 13.48 12.04 ______________________________________
It has also been found that the aminophosphites according to the invention can be hydrolysed to form ammonium salts of monoalkyl phosphites in accordance with the following scheme: ##STR2##
These .beta.-hydroxy ethyl phosphite salts are also fungicidal and are the subject of French Patent Application for Patent of Addition No. 73-37.994.